EP0043952B1 - Masses intumescentes éventuellement mousseuses - Google Patents

Masses intumescentes éventuellement mousseuses Download PDF

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Publication number
EP0043952B1
EP0043952B1 EP81104882A EP81104882A EP0043952B1 EP 0043952 B1 EP0043952 B1 EP 0043952B1 EP 81104882 A EP81104882 A EP 81104882A EP 81104882 A EP81104882 A EP 81104882A EP 0043952 B1 EP0043952 B1 EP 0043952B1
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EP
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Prior art keywords
parts
intumescent
weight
polyisocyanates
foam
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Expired
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EP81104882A
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German (de)
English (en)
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EP0043952A3 (en
EP0043952A2 (fr
Inventor
Wulf Dr. Von Bonin
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Bayer AG
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Bayer AG
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Priority to AT81104882T priority Critical patent/ATE6263T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings

Definitions

  • the invention relates to intumescent compositions based on foamed or non-foamed polyurethanes which contain aromatic hydroxycarboxylic acids as a recipe component.
  • Intumescent masses are masses which foam when exposed to fire and heat and thereby form an insulating and fire-repellent foam which protects the rear areas from the effects of fire.
  • Such intumescent materials are known in the form of lacquers, coatings and mortars or putties.
  • intumescent materials corresponding to the prior art do meet some of the requirements mentioned, but no intumescent material is known which meets all of these requirements.
  • the present invention provides such intumescent materials.
  • a polyisocyanate with 100 parts by weight of a mixture consisting of 25 to 80% by weight of phosphorus-containing condensation products containing at least two hydroxyl groups and 10 to 65% by weight of hydroxycarboxylic acids or their salts and 0 to 8 , 5 wt .-% water and / or 0 to 50 wt .-% of further organic compounds with isocyanate-reactive hydrogen atoms.
  • foams of this type which are produced in this way, foam vigorously in the heating test described and in the flame, but also foams with low densities, for example between 40 and 400 kg / m 3. It is also surprising that the polyurethane products, for example preheated to 260 ° C., subsequently Exposure to elevated temperatures, eg with a flame are able to foam again.
  • the polyurethanes accessible according to the invention even if they are in the form of foams with a high surface area, do not become ineffective in relation to their use as intumescent compositions by storing water.
  • the present invention makes it possible to use intumescent materials in the form of foams, as a result of which not only the intumescent material itself can function as a thermal insulating material even without heat stress, but also completely new design options for intumescent substances.
  • the hard, e.g. Types present as foams can be thermoplastic at temperatures below their decomposition point, i.e. without loss of their intumescent effect, i.e. deform at temperatures between 180 and 200 ° C. This surprising behavior allows e.g. the pressing into molded parts or the transformation of foam pre-products into new molded parts.
  • the new intumescent materials can be manufactured continuously or discontinuously.
  • the production can take place by mixing the components or already pre-mixed component mixtures on site and the reaction mixture can be made by machine or by hand in e.g. openings to be closed or heated or unheated molds are poured in, where they then foam or harden. With appropriate technical equipment, it can be sprayed, spread on or poured onto the substrates and substrates to be protected.
  • semi-finished products e.g. Manufactures foams or coatings and then processes them in a technically required manner, e.g. by cutting, by thermoforming, granulating, grinding or mixing.
  • foamed or solid inorganic or organic additives e.g. Polystyrene foam, polyurethane foam or gravel or expanded clay, urea or phenolic resin foams, foam glass, wood, mineral wool, pumice, etc.
  • foamed or solid inorganic or organic additives e.g. Polystyrene foam, polyurethane foam or gravel or expanded clay, urea or phenolic resin foams, foam glass, wood, mineral wool, pumice, etc.
  • foamed or solid inorganic or organic additives e.g. Polystyrene foam, polyurethane foam or gravel or expanded clay, urea or phenolic resin foams, foam glass, wood, mineral wool, pumice, etc.
  • foamed or solid inorganic or organic additives e.g. Polystyrene foam, polyurethane foam or gravel or expanded clay, urea or phenolic resin foams, foam glass, wood, mineral wool, pumice, etc.
  • triphenylmethane-4,4 ', 4 "-triisocyanate polyphenyl-polymethylene polyisocyanates as obtained by aniline-formaldehyde condensation and subsequent phosgenation and are described, for example, in GB Patents 874430 and 848671, m- and p-isocyanatophenylsulfonyl isocyanates according to US Pat. No. 3,454,606, perchlorinated aryl polyisocyanates, as described, for example, in German Patent Application No. 1,157,601 (US Pat. No. 3,277,138), polyisocyanates containing carbodiimide groups, as described in German Patent No.
  • distillation residues obtained in the industrial production of isocyanates and containing isocyanate groups optionally dissolved in one or more or the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
  • polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers ( «TDI»), but especially polyphenylpolymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ( «crude MDI»), as well as carbodiimide groups , Urethane groups, allophanate groups, isocyanaturate groups, urea groups or biuret groups-containing polyisocyanates (“modified polyisocyanates”), in particular those modified polyisocyanates derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4′- and / or derive 2,4'-diphenylmethane diisocyanate.
  • modified polyisocyanates modified polyisocyanates
  • At least two phosphorus-containing condensation products containing hydroxyl groups such as those e.g. can be obtained by condensation of primary or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic mono- and / or polyamines, carbonyl compounds and dialkylphosphites, optionally with subsequent OH groups, optionally followed by oxalkylation.
  • condensation products are known per se, e.g. from DE-PS 1143022, US-PS 3076010, DE-AS 1 803 747 and DE-AS 1 928 265.
  • Aromatic hydroxycarboxylic acids or their salts e.g. Hydroxy-naphthalene-carboxylic acids, salicylic acid, m-hydroxybenzoic acid and / or p-hydroxybenzoic acid.
  • Nucleus-substituted e.g. Alkylated hydroxybenzenecarboxylic acids or acetylation products or anhydrides of the hydroxycarboxylic acids are also suitable. According to the invention, hydroxybenzoic acids and / or their salts are preferred.
  • Suitable salts of the aromatic hydroxycarboxylic acids are, for example, the alkali metal salts, alkaline earth metal salts, but in particular the amine salts.
  • the amines to be used for salt formation in addition to NH 3 , those with low vapor pressure are preferred, for example alkoxylation products of ammonia with propylene oxide, but especially ethylene oxide, such as ethanolamine, diethanolamine and triethanolamine.
  • salt formers are the alkoxylation products of other amines, for example N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine or the alkali or alkaline earth metal hydroxides.
  • the degree of neutralization of the aromatic hydroxycarboxylic acids in relation to the use of the salt formers just mentioned is generally below 100%, preferably between 0 and 75%.
  • the hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
  • polyhydric preferably dihydric and optionally additionally trihydric alcohols
  • polyhydric preferably dihydric, carboxylic acids.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated.
  • the at least two, usually two to eight, preferably two to three, hydroxyl group-containing polyethers which are suitable according to the invention are also of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of Lewis catalysts such as BF 3 , or by addition of these epoxides, preferably of ethylene oxide and propylene oxide, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
  • Lewis catalysts such as BF 3
  • these epoxides preferably of ethylene oxide and propylene oxide, optionally in
  • Sucrose polyethers such as are described, for example, in DE-A-1 176 358 and 1 064 938, and polyethers started on formite or formose (DE laid-open publications 2 639 083 and 2 737 951) are also suitable according to the invention.
  • mixtures of different compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32 to 400 can be used.
  • mixtures of hydroxyaldehydes and hydroxyketones (“formose”) or the polyhydric alcohols (“formite”) obtained therefrom by reduction are also suitable as low molecular weight polyols, such as those used in the self-condensation of formaldehyde hydrate in the presence of metal compounds as a catalyst and of Compounds capable of endiol formation are formed as cocatalysts (German Offenlegungsschriften 2,639,084, 2,714,084, 2714104, 2721 186, 2738154 and 2738512).
  • Aliphatic diamines suitable according to the invention are, for example, ethylenediamine, 1,4-tetramethylenediamine, 1,11 -undecamethylenediamine, 1,12-dodecamethylenediamine and mixtures thereof, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane ("isophoronediamine”), 2,4- and 2,6-hexahydrotoluenediamine and their mixtures, perhydro-2,4'- and 4,4'-diaminodiphenylmethane, p-xylylenediamine, bis- (3-aminopropyl) methylamine, diamino-perhydroanthrazenes (German Offenlegungsschrift 2638731) and cycloaliphatic triamines according to DE Offenlegungsschrift 2,614,244.
  • hydrazine and substituted hydrazines for example Methylhydrazine, N, N'-dimethylhydrazine, their homologues and acid dihydrazides are suitable according to the invention.
  • aromatic diamines are bisanthranilic acid esters according to DE-Offenlegungsschriften 2,040,644 and 2,160,590, 3,5- and 2,4-diaminobenzoic acid esters according to DE-Offenlegungsschrift 2025900, which are described in DE-Offenlegungsschriften 1 803 635 (US Pat. Nos.
  • a particularly suitable type of polyol according to the invention are the esters of 1.5-2 moles of ethylene glycol and 1 mole of benzenedicarboxylic acid, e.g. Phthalic acid, average molecular weight approx. 250-600. It was found that the advantageous properties of the new intumescent materials, in particular intumescent foams, are not characteristic of the stoichiometric ratios customary for conventional polyurethane chemistry.
  • reaction mixture 100 parts by weight of this reaction mixture are generally reacted with 50 to 180, preferably 65 to 150 parts by weight of the polyisocyanate.
  • the intumescent materials can be produced in a solvent, but preferably without solvent.
  • the preferred products are foams; these can have densities of approximately 15 to 800 kg / m 3 , preferably between 60 and 300 kg / m 3 .
  • a particularly balanced combination between the desired low density for reasons of insulation ability and the mass necessary for the foaming effect in the event of flame in the room unit are, according to the invention, accessible foams with densities of approx. 80 to 200 kg / m 3 .
  • the different reaction components can be brought together individually; Expediently, however, a premix is made from components 2, 3 and optionally 4 which are reactive with the polyisocyanates (component 1), and a liquid reaction component, which is usually in the form of a solution and contains all the necessary constituents except for the polyisocyanate, is obtained after brief heating .
  • a premix is made from components 2, 3 and optionally 4 which are reactive with the polyisocyanates (component 1), and a liquid reaction component, which is usually in the form of a solution and contains all the necessary constituents except for the polyisocyanate, is obtained after brief heating .
  • a liquid reaction component which is usually in the form of a solution and contains all the necessary constituents except for the polyisocyanate
  • component premix possibly also to the isocyanate, e.g. Melamine, melamine condensates, urea-formaldehyde condensates, melamine phosphates, amine polyphosphates, phosphoric acid esters e.g. Tricresyl phosphate or dibutyl cresyl phosphate, Al oxide hydrates, glass powder, solid or hollow glass or other silicate beads and other additives that modify the fire behavior.
  • isocyanate e.g. Melamine, melamine condensates, urea-formaldehyde condensates, melamine phosphates, amine polyphosphates, phosphoric acid esters e.g. Tricresyl phosphate or dibutyl cresyl phosphate, Al oxide hydrates, glass powder, solid or hollow glass or other silicate beads and other additives that modify the fire behavior.
  • isocyanate e.g. Melamine, melamine condensates, ure
  • a material sample (8 x 4 x 2 cm) was stored under tap water for three days, then the water was poured off and replaced with new water. After a further three days, the water was poured off, the test specimen was thrown off and dried back at 75 ° C. Before and after drying, it was checked whether there was a significant change in volume (edge length) or a greater change in strength with centimeter dimensions or by manual inspection. The redried samples were subjected to Tests I, II and 111.
  • the foams according to example 1 are flame retardant in the same way as the sample from comparison 1, i.e. in the afterburn test they are classified as short: afterburning briefly, i.e. they extinguish within 3 seconds after the flame has been removed.
  • a good intumescent foam should at least still be able to foam if it is not already foamed.
  • these panels can be used as insulation panels with an intumescent character or can be thermoplastic molded.
  • 2 cm thick sheets of the intumescent foam are heated to approx. 150 ° C in the heating cabinet (high-frequency, microwave or infrared heating is also possible) and then e.g. on a gauge bent into tubes, half-shells that retain their shape after cooling. It is also possible to compact the plates on a heated press at approx. 130 ° C.
  • component C1 is replaced by component C2 or C3, the densities of the available foams change, but not their intumescent properties.
  • Example 4 The procedure is as in Example 4, but 10 parts of a polyester of adipic acid and ethylene glycol (molecular weight approx. 2000) and 40 parts of compo are added to the premix nente C1 added.
  • the resulting rigid foam has a density of 145 kg / m 3 .
  • the classifications are obtained before and after the water storage test according to test 111.
  • component A 100 parts of component A are converted into a solution with 20 parts of salicylic acid, 30 parts of 4-hydroxybenzoic acid and 25 parts of isopropanol (B2). 40 parts of this solution are reacted with 30 parts of the isocyanate described in comparison 1. A highly viscous material is formed, which is insoluble in water, but is soluble in isopropanol.
  • a 50% isopropanol solution of the reaction product is prepared.
  • a steel plate is coated with this solution and the coating formed is dried at 150 ° C. in 30 minutes to form a hard, insoluble film.
  • an insulating, fire-repellent foam develops due to the intumescence reaction.
  • the isopropanol solution can also be converted into an emulsion with water, from which the isopropanol can optionally be removed by thin layering.
  • emulsions are well suited for painting purposes.
  • reaction mixture foams in the cavity and fills all gussets between cables, route and masonry. Foam emerging from the opening is cut off after hardening. In the test, the foam achieved the same classification before and after water storage:
  • Example 7 The 60% isopropanol solution obtained according to Example 7 is mixed with 50% (based on the solids content) of melamine powder and the viscous mixture thus obtained is applied to an asbestos cement board. After drying out (30 days in the laboratory), test 111 is carried out on the dry coating:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Medicines Containing Plant Substances (AREA)

Claims (5)

1. Matières intumescentes éventuellement transformées en mousse, obtenues par réaction
1. de polyisocyanates avec
2. des produits de condensation contenant du phosphore portant au moins deux groupes hydroxyle, pouvant être obtenus par condensation de mono- et/ou de polyamines primaires ou secondaires aliphatiques, cycloaliphatiques, aromatiques, araliphatiques ou hétérocycliques renfermant éventuellement des groupes OH, de composés carbonyliques et de phosphites de dialkyle, le cas échéant avec oxalkylation subséquente, et
3. des acides hydroxycarboxyliques aromatiques ou leurs sels et
4. éventuellement de l'eau et/ou d'autres composés organiques portant des atomes d'hydrogène aptes à réagir vis-à-vis d'isocyanates.
2. Matières intumescentes suivant la revendication 1, obtenues par réaction de 50 à 180 parties en poids d'un polyisocyanate avec 100 parties en poids d'un mélange formé de 20 à 80% en poids de produits de condensation contenant du phosphore portant au moins deux groupes hydroxyle et 10 à 65% en poids d'acides hydroxycarboxyliques ou leurs sels et 0 à 8,5% en poids d'eau et/ou 0 à 50% en poids d'autres composés organiques portant des atomes d'hydrogène aptes à réagir vis-à-vis d'isocyanates.
3. Matières intumescentes suivant les revendications 1 et 2, caractérisées en ce qu'on utilise comme polyisocyanates des polyisocyanates tels qu'on en obtient par condensation aniline-formaldéhyde et phosgénation subséquente.
4. Matières intumescentes suivant les revendications 1 à 3, caractérisées en ce qu'on utilise comme produits de condensation portant au moins deux groupes hydroxyle des produits de formule
Figure imgb0026
dans laquelle
R = alkyle en Ci à C8 ou hydroxyalkyle en Ci à Cget
X = H ou méthyle.
5. Matières intumescentes suivant les revendications 1 à 4, caractérisées en ce qu'on utilise comme acides hydroxycarboxyliques aromatiques des acides hydroxybenzoiques.
EP81104882A 1980-07-04 1981-06-24 Masses intumescentes éventuellement mousseuses Expired EP0043952B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81104882T ATE6263T1 (de) 1980-07-04 1981-06-24 Gegebenenfalls geschaeumte intumeszenzmassen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803025309 DE3025309A1 (de) 1980-07-04 1980-07-04 Gegebenenfalls geschaeumte intumeszenzmassen
DE3025309 1980-07-04

Publications (3)

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EP0043952A2 EP0043952A2 (fr) 1982-01-20
EP0043952A3 EP0043952A3 (en) 1982-01-27
EP0043952B1 true EP0043952B1 (fr) 1984-02-15

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US (1) US4338412A (fr)
EP (1) EP0043952B1 (fr)
JP (1) JPS5747320A (fr)
AT (1) ATE6263T1 (fr)
AU (1) AU7214181A (fr)
DE (2) DE3025309A1 (fr)
ES (1) ES503646A0 (fr)
ZA (1) ZA814528B (fr)

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WO2014056865A2 (fr) 2012-10-11 2014-04-17 Hilti Aktiengesellschaft Manchon coupe-feu
DE102013200546A1 (de) 2013-01-16 2014-07-17 Hilti Aktiengesellschaft Akkumulator für eine Handwerkzeugmaschine und Verfahren zum Herstellen eines Akkumulators für eine Handwerkzeugmaschine
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EP2827041A1 (fr) 2013-07-18 2015-01-21 HILTI Aktiengesellschaft Matériau d'isolation et isolation pour un tuyau dans la zone d'un passage de mur ou de plafond
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EP3088785A1 (fr) 2015-04-27 2016-11-02 Hilti Aktiengesellschaft Manchette coupe-feu
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DE3109352A1 (de) * 1981-03-12 1982-09-23 Bayer Ag, 5090 Leverkusen Gegebenenfalls geschaeumte intumeszenzmassen und ihre verwendung
DE3235571A1 (de) * 1982-09-25 1984-03-29 Bayer Ag, 5090 Leverkusen Gegebenenfalls geschaeumte intumeszenzmassen und ihre verwendung
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DE102011007654A1 (de) * 2011-04-19 2012-11-08 Hilti Aktiengesellschaft Komprimierbares Weichschott, Verfahren zu seiner Herstellung und seine Verwendung
DE102011007654B4 (de) * 2011-04-19 2012-12-06 Hilti Aktiengesellschaft Komprimierbares Weichschott, Verfahren zu seiner Herstellung und seine Verwendung
EP2570157A2 (fr) 2011-09-19 2013-03-20 HILTI Aktiengesellschaft Elément ignifuge
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WO2014056865A2 (fr) 2012-10-11 2014-04-17 Hilti Aktiengesellschaft Manchon coupe-feu
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Also Published As

Publication number Publication date
EP0043952A3 (en) 1982-01-27
US4338412A (en) 1982-07-06
DE3162273D1 (en) 1984-03-22
DE3025309A1 (de) 1982-02-04
JPS5747320A (en) 1982-03-18
ES8301490A1 (es) 1982-12-01
EP0043952A2 (fr) 1982-01-20
ES503646A0 (es) 1982-12-01
ZA814528B (en) 1982-07-28
AU7214181A (en) 1982-01-07
ATE6263T1 (de) 1984-03-15

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